Dye-sensitized photoelectric transducer

ABSTRACT

The present invention relates to an organic dye-sensitized semiconductor device and to a solar cell using it and, particularly, to a photoelectric conversion device using semiconductor fine particles sensitized with a dye having an acrylic acid part and a solar cell using it. According to the present invention, a low-cost photoelectric conversion device having favorable conversion efficiency and a solar cell can be obtained.

TECHNICAL FIELD

[0001] The present invention relates to photoelectric conversion devicesusing semiconductor fine particles sensitized with organic dye(s) andsolar cells using semiconductor fine particles sensitized with organicdye(s), and in particular to a photoelectric conversion devicecharacterized by using oxide semiconductor fine particles sensitizedwith a dye having an acrylic acid part(s) and a solar cell utilizing thesame.

BACKGROUND OF THE INVENTION

[0002] A solar cell utilizing sunlight as an alternative energy sourceto a fossil fuel such as petroleum, coal or the like has been in thespot light. Today, developments and studies are being conducted onenhancement of efficiency and the like of a silicon solar cell whichuses crystalline or amorphous silicon, a compound semiconductor solarcell which uses gallium, arsenic or the like. However, since much energyis required for producing these solar cells and the cost of them ishigh, there is a problem that it is difficult to put them to generaluse. Further, a photoelectric conversion device which uses semiconductorfine particles sensitized with dye(s) and a solar cell which uses thisdevice have been known whereupon materials for use in producing them andtechniques for producing them have been disclosed. (B. O'Regan and M.Gratzel Nature, 353, 737 (1991), M. K. Nazeeruddin, A. Kay, I. Rodicio,R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Gratzel, J.Am. Chem. Soc., 115, 6382 (1993) e.t.c.). This photoelectric conversiondevice is produced by using a comparatively low-cost oxide semiconductorsuch as titanium oxide or the like. Since there is a possibility that aphotoelectric conversion device can be obtained in low cost comparedwith a solar cell which uses a conventional silicon or the like, thisdevice has been remarked. However, in order to obtain a device havinghigh conversion efficiency, a ruthenium-type complex is used as asensitizing-dye wherein the dye itself is high in cost and there also isa problem in supply thereof. Further, although it has already beenattempted to use an organic dye as a sensitizing-dye, it is a presentsituation that, due to low conversion efficiency and the like, it hasnot yet been used practically.

[0003] A development of a photoelectric conversion device, using anorganic dye-sensitized semiconductor, which has high conversionefficiency as well as high practicability has been required.

DISCLOSURE OF THE INVENTION

[0004] The present inventors have made an extensive effort to solve theabove-described problems and, as a result, have found that aphotoelectric conversion device having high conversion efficiency can beobtained by sensitizing semiconductor fine particles with a dye havingan acrylic acid part and, then, producing a photoelectric conversiondevice to achieve the present invention.

[0005] Namely, the present invention relates to

[0006] (1) a photoelectric conversion device, characterized bycomprising oxide semiconductor fine particles sensitized with a dyehaving an acrylic acid part,

[0007] (2) a photoelectric conversion device, characterized bycomprising oxide semiconductor fine particles sensitized with a dyerepresented by the following formula (1) having an acrylic acid part:

[0008] wherein A1 and A2 each independently represent a carboxyl group,a cyano group, an alkoxycarbonyl group, an acyl group, a nitro group, acyclic hydrocarbon residue which may be substituted, a heterocyclicresidue which may be substituted, an amino group which may besubstituted, a hydroxyl group, a hydrogen atom, a halogen atom or analkyl group which may be substituted; X represents an aromatichydrocarbon residue which may be substituted, a heterocyclic residuewhich may be substituted, an organic metal complex residue which may besubstituted or an amino group which may be substituted,and, when n is 2or more, that is, a plurality of A1 and a plurality of A2 are present,each A1 and each A2 independently represent any one of theabove-described groups which may be same with or different from eachother, and further two among of A1s or each A1 in a plurality of A1, A2or each A2 in a plurality of A2 and X may be bound together to form aring which may be substituted,

[0009] (3) the photoelectric conversion device as mentioned in theabove-described (2), wherein n is from 1 to 3 in the formula (1),

[0010] (4) the photoelectric conversion device as mentioned in theabove-described (2), characterized by that at least one of A1 and A2 or,when plural A1s and plural A2s are present, at least one thereof is acyano group or a carboxyl group in the formula (1),

[0011] (5) the photoelectric conversion device as mentioned in theabove-described (4), characterized by that A1 in the formula (1) is acyano group or a carboxyl group wherein the A1 binds to the same carbonatom as that the carboxyl group in an acrylic part is bound to.

[0012] (6) the photoelectric conversion device as mentioned in any oneof the above-described (2) to (5), wherein the aromatic hydrocarbonresidue in X in the formula (1) is an aromatic hydrocarbon residuehaving a substituted amino group,

[0013] (7) the photoelectric conversion device as mentioned in any oneof the above-described (2) to (5), wherein the heterocyclic residue is aheterocyclic residue which is a 5- or 6-membered ring containing from 1to 3 hetero atoms and may be substituted, or a heterocyclic residuecomprising a condensed ring, having from 8 to 15 carbon atoms, whichcontains a 5- or 6-membered heterocycle containing from 1 to 3 heteroatoms,

[0014] (8) the photoelectric conversion device as mentioned in theabove-described (6), wherein the aromatic hydrocarbon residue in X ofthe formula (1) is an aromatic hydrocarbon residue comprising anaromatic ring having from 6 to 16 carbon atoms,

[0015] (9) the photoelectric conversion device as mentioned in theabove-described (8), wherein the aromatic hydrocarbon residue in X ofthe formula (1) is a phenyl group having a mono- or di-(C1 to C4)alkyl-substituted amino group, wherein the above-described phenyl groupmay further be substituted by one or two substituents selected from thegroup consisting of a halogen atom, an alkyl group having from 1 to 4carbon atoms and an alkoxy group having from 1 to 4 carbon atoms,

[0016] (10) the photoelectric conversion device as mentioned in any oneof the above-described (1) to (9), characterized by comprising oxidesemiconductor fine particles sensitized with simultaneously two or moresensitizing-dyes comprising at least one dye having an acrylic acidpart,

[0017] (11) the photoelectric conversion device as mentioned in theabove-described (10), characterized by comprising oxide semiconductorfine particles sensitized with simultaneously three or more types ofsensitizing-dyes,

[0018] (12) the photoelectric conversion device as mentioned in any oneof the above-described (1) to (11), wherein the oxide semiconductor fineparticles comprise titanium dioxide as an essential component,

[0019] (13) the photoelectric conversion device as mentioned in any oneof the above-described (1) to (12), wherein a dye is adsorbed to theoxide semiconductor fine particles in the presence of an inclusioncompound, and

[0020] (14) a solar cell, characterized by comprising the photoelectricconversion device as mentioned in any one of the above-described (1) to(13).

BEST MODE FOR CARRYING OUT THE INVENTION

[0021] The present invention will be described in detail below. Aphotoelectric conversion device according to the present invention usesan oxide semiconductor sensitized with a dye having an acrylic acidpart. The dye having an acrylic acid part to be used in the presentinvention is not particularly limited, so long as the dye has an acrylicacid part, but, as being a favorable dye, is mentioned a dye representedby the following general formula (1):

[0022] wherein A1, A2, X and n each have the same meaning as describedabove.

[0023] Unless stated otherwise, the term “dye” herein represented by thegeneral formula (1) is intended to mean any one of a free acid and asalt thereof represented by the general formula (1).

[0024] Examples of salts of compounds represented by the general formula(1) include a metallic salt of a carboxylic acid portion of theabove-described formula, for example, a salt with an alkali metal,alkali earth metal or the like such as lithium, sodium, potassium,magnesium, calcium or the like, and a salt such as a quaternary ammoniumsalt such as an organic base, for example, tetramethyl ammonium,tetrabutyl ammonium, pyridinium, imidazolium or the like.

[0025] Further, A1 and A2 each independently represent a carboxyl group,a cyano group, an alkoxycarbonyl group, an acyl group, a nitro group, acyclic hydrocarbon residue which may be substituted, a heterocyclicresidue which may be substituted, an amino group which may besubstituted, a hydroxyl group, a hydrogen atom, a halogen atom or analkyl group which may be substituted. Furthermore, when a plurality ofA1 and a plurality of A2 are present, each A1 and each A2 independentlyrepresent the above-described groups which may be identical with ordifferent from each other.

[0026] As substituents in the cyclic hydrocarbon residue which may besubstituted and the heterocyclic residue which may be substituted,mentioned are, but not particularly limited to, an alkyl group, an arylgroup, a cyano group, an isocyano group, a thiocyanato group, anisothiocyanato group, a nitro group, a nitrosyl group, an acyl group, ahalogen atom, a hydroxyl group, a phosphoric acid group, a phosphoricacid ester group, a mercapto group which may be or may not besubstituted, an amino group which may be or may not be substituted, anamide group which may be or may not be substituted, an alkoxyl group, analkoxyalkyl group, a carboxyl group, an alkoxycarbonyl group, a sulfogroup and the like.

[0027] As alkyl groups, mentioned are saturated and unsaturated groupsof straight-chain, branched-chain and cyclic types which may besubstituted, wherein, they have preferably from 1 to 36 carbon atoms,and more preferably it is the straight-chain saturated alkyl grouphaving from 1 to 20 carbon atoms which may be substituted. As the cyclicgroup, mentioned are, for example, a cycloalkyl having from 3 to 8carbon atoms and the like. These alkyl groups may further be substitutedby the above-described substituents (except alkyl groups).

[0028] As aryl groups, mentioned are groups, in which a hydrogen atom isremoved from an aromatic ring, mentioned in the part of cyclichydrocarbon residues mentioed below and the like. The aryl groups mayfurther be substituted by the above-described groups or the like.

[0029] Examples of acyl groups include an alkyl carbonyl group havingfrom 1 to 10 carbon atoms, an aryl carbonyl group and the like, andpreferably the alkyl carbonyl group having from 1 to 4 carbon atoms. Asa specific example, mentioned are an acetyl group, a propionyl group andthe like.

[0030] As halogen atoms, mentioned are chlorine, bromine, iodine atomsand the like.

[0031] As phosphoric acid ester groups, mentioned are a phosphoric acid(C1 to C4) alkyl ester and the like.

[0032] As mercapto groups which are substituted or un substituted,mentioned are a mercapto group, an alkyl mercapto group and the like.

[0033] As amino groups which are substituted or unsubstituted, mentionedare an amino group, a mono- or dialkyl amino group, a mono- ordiaromatic amino group and the like, and, as those, mentioned are amono-or dimethyl amino group, amono- or diethyl amino group, a mono- ordipropyl amino group, a monophenyl amino group, a benzyl amino group andthe like.

[0034] As amide groups which are substituted or unsubstituted, mentionedare an amide group, an alkyl amide group, an aromatic amide group andthe like.

[0035] Examples of alkoxyl groups include an alkoxyl group having from 1to 10 carbon atoms and the like.

[0036] Examples of alkoxyalkyl groups include a (C1 to C10) alkoxy (C1to C4) alkyl group and the like.

[0037] Examples of alkoxycarbonyl groups include an alkoxycarbonyl grouphaving from 1 to 10 carbon atoms and the like.

[0038] Further, acidic groups such as a carboxyl group, a sulfo group, aphosphoric acid group and the like may be in a state in which they formsalts, for example, salts of metals such as lithium, sodium, potassium,magnesium, calcium and the like, and quaternary ammonium salts such astetramethyl ammonium, tetrabutyl ammonium, pyridinium, imidazolium andthe like.

[0039] The cyclic hydrocarbon residue means a group obtained by removinga hydrogen atom from a cyclic hydrocarbon.

[0040] Examples of cyclic hydrocarbons include benzene, naphthalene,anthracene, phenanthrene, pyrene, indene, azulene, fluorene,cyclohexane, cyclopentane, cyclohexene, cyclopentene, cyclohexadiene,cyclopentadiene and the like and as cyclic hydrocarbon residues,mentioned are groups obtained by removing a hydrogen atom from each ofthese cyclic hydrocarbons.

[0041] The heterocyclic residue means a group obtained by removing ahydrogen atom from a heterocyclic compound and, as heterocyclicresidues, illustrated are those mentioned in the part of heterocyclicresidues represented by X mentioned below and the like. Examples ofpreferable heterocyclic residues in A1 or A2 include residues obtainedby removing a hydrogen atom from each of cyclic compounds such aspyridine, pyrazine, piperizine, morpholine, indoline, thiophene, furan,oxazole, thiazole, indole, benzothiazole, benzoxazole, pyrazine,quinoline and the like, and these residues may be substituted asdescribed above.

[0042] Further, A1 and A2 may be bound with each other to form a ring.Particularly, when n mentioed below is 2 or more and A1 and A2 are eachpresent in a plurality number, any two thereof may be bound with eachother to form a ring. When,a ring is formed, any one of A1 and any oneof A2 may be bound with each other without any specific limitation;however, ordinarily, adjacent A1 and A2, adjacent two A1 or adjacent twoA2 form the ring therebetween. The above-described ring may besubstituted. As substituents in a case in which such substituents may behad, mentioned are substituents described in the part of theabove-described cyclic hydrocarbon residues which may be substituted. Asa ring which is formed by allowing A1 and A2, or any one of A1s whichare present in a plural number and any one of A2s which are present in aplural number to be bound with each other, mentioned are an unsaturatedhydrocarbon ring or a heterocycle. As such unsaturated hydrocarbonrings, mentioned are a benzene ring, a naphthalene ring, an anthracenering, a phenanthrene ring, a pyrene ring, an indene ring, an azulenering, a fluorene ring, a cyclobutene ring, a cyclopentene ring, acyclohexene ring, a cyclohexadiene ring, a cyclopentadiene ring and thelike; as such heterocycles, mentioned are a pyridine ring, a pyrazinering, an indoline ring, a thiophene ring, a furan ring, a pyran ring, anoxazole ring, a thiazole ring, an indole ring, a benzothiazole ring, abenzoxazole ring, a pyrazine ring, a quinoline ring, a carbazole ring, abenzopyran ring and the like. Among these rings, the cyclobutene ring,the cyclopentene ring, the cyclohexene ring, the pyran ring and the likeare preferable. Further, when A1 or A2 has a carbonyl group, athiocarbonyl group or the like, a cycloketone, a cyclothioketone or thelike may be formed. Examples of compounds which form these rings includecompounds exemplified in the compound from No. 110 to compound No. 118,No. 127 and No. 131 and the like mentioed below.

[0043] Preferably A1 and A2 are each independently a carboxyl group, acyano group, an alkoxycarbonyl group, an acyl group, a hydroxyl group, ahydrogen atom, a halogen atom or an alkyl group. Among these groups, thecarboxyl group, the cyano group, the hydrogen atom, the halogen atom,the alkyl group are more preferable. Among such halogen atoms, achlorine atom, a bromine atom and an iodine atom are preferable.Further, when, in the formula (1), A1 is bound to a same carbon atom asthat the carboxyl group is bound to, the carboxyl group or the cyanogroup is particularly preferable.

[0044] n is an integer of from 1 to 6.

[0045] When n is 1, the general formula (1) is represented by thefollowing formula (2):

[0046] wherein B1 and B2 each independently represent a carboxyl group,a cyano group, an alkoxycarbonyl group, an acyl group, a nitro group, acyclic hydrocarbon residue which may be substituted, a heterocyclicresidue which may be substituted, an amino group which may besubstituted, a hydroxyl group, a hydrogen atom, a halogen atom or analkyl group which may be substituted, and further a ring which may besubstituted may be formed by using a number of parts of B1, B2 or X; andX represents an aromatic hydrocarbon residue which may be substituted, aheterocyclic residue which may be substituted, an organic metal complexresidue which may be substituted or an amino group which may besubstituted. Substituent(s) in B1 and B2 may be the same as thosementioned in the above-described A1 and A2. As preferable combinationsamong these B1 and B2, mentioned are combinations that B1 is a carboxylgroup, a cyano group or a hydroxyl group and B2 is a carboxyl group, acyano group, a halogen atom, an alkyl group or a hydrogen atom. As morepreferable combinations, mentioned are combinations that B1 is acarboxyl group or a cyano group and B2 is a hydrogen atom.

[0047] When n is 2, the general formula (1) is represented by thefollowing formula (3):

[0048] wherein C1, C2, C3 and C4 each independently represent a carboxylgroup, a cyano group, an alkoxycarbonyl group, an acyl group, a nitrogroup, a cyclic hydrocarbon residue which may be substituted, aheterocyclic residue which may be substituted, an amino group which maybe substituted, a hydroxyl group, a hydrogen atom, a halogen atom or analkyl group which may be substituted, and a ring which may besubstituted may be formed by using a number of parts of C1, C2, C3, C4or X; and X represents an aromatic hydrocarbon residue which may besubstituted, a heterocyclic residue which may be substituted, an organicmetal complex residue which may be substituted or an amino group whichmay be substituted. C1, C2, C3 and C4 represent the same groups as thosementioned in the above-described A1 and A2 whereupon substituents andthe like are also the same as those mentioned in the above-described A1and A2. As preferable combinations among these groups, mentioned arecombinations that C1 is a carboxyl group, a cyano group, analkoxycarbonyl group, an acyl group or a hydroxyl group, and C2, C3 andC4 each independently are a carboxyl group, a cyano group, a halogenatom, an alkyl group or a hydrogen atom. As more preferablecombinations, mentioned are combinations that C1 is a carboxyl group ora cyano group, and C2, C3 and C4 are hydrogen atoms.

[0049] When n is 3, the general formula (1) is represented by thefollowing formula (4):

[0050] wherein D1, D2, D3, D4, D5 and D6 each independently represent acarboxyl group, a cyano group, an alkoxycarbonyl group, an acyl group, anitro group, a cyclic hydrocarbon residue which may be substituted, aheterocyclic residue which,may be substituted, an amino group whichmaybe substituted, a hydroxyl group, a hydrogen atom, a halogen atom oran alkyl group which may be substituted, wherein a ring which may besubstituted may be formed by using a number of parts of D1, D2, D3, D4,D5, D6 or X; and X represents an aromatic hydrocarbon residue which maybe substituted, a heterocyclic residue which may be substituted, anorganic metal complex residue which may be substituted or an amino groupwhich may be substituted. D1, D2, D3, D4, D5 and D6 represent samegroups as those mentioned in the above-described A1 and A2 whereuponsubstituents and the like are also same as those mentioned in theabove-described A1 and A2. As preferable combinations among thesegroups, mentioned are combinations that D1 is a carboxyl group, a cyanogroup, an alkoxycarbonyl group, an acyl group or a hydroxyl group, andD2, D3, D4, D5 and D6 each independently are a carboxyl group, a cyanogroup, a halogen atom, an alkyl group or a hydrogen atom. As morepreferable combinations, mentioned are combinations that D1 is acarboxyl group or a cyano group, and D2, D3, D4, D5 and D6 are hydrogenatoms.

[0051] X represents an aromatic hydrocarbon residue which may besubstituted, a heterocyclic residue which may be substituted, an organicmetal complex residue which may be substituted or an amino group whichmay be substituted.

[0052] The aromatic hydrocarbon residue means a group obtained byremoving a hydrogen atom from an aromatic hydrocarbon. As the groupobtained by removing a hydrogen atom from an aromatic hydrocarbon,mentioned are for example benzene, naphthalene, anthracene,phenanthrene, pyrene, indene, azulene, fluorene and the like and thesegroups each may be substituted as described above. Each of thesearomatic hydrocarbon residues ordinarily has an aromatic ring (aromaticring and condensation ring containing an aromatic ring or the like)having from 6 to 16 carbon atoms.

[0053] As the heterocyclic residue which may be substituted, mentionedis a group obtained by removing a hydrogen atom from a heterocycliccompound which may be substituted. Examples of such heterocycliccompounds include pyridine, pyrazine, pyrimidine, pyrazole,pyrazolidine, thiazolidine, oxazolidine, pyran, chromene, pyrrole,benzimidazole, imidazoline, imidazolidine, imidazole, pyrazole,triazole, triazine, diazole, morpholine, indoline, thiophene, furan,oxazole, thiazine, thiazole, indole, benzothiazole, naphthothiazole,benzoxazole, naphthoxazole, indolenine, benzoindolenine, pyrazine,quinoline, quinazoline, carbazole and the like, and these compounds mayhave been subjected to ring-increasing or hydrogenation and saidcompounds may be substituted.

[0054] Further, when X is a heterocycle or the like, the heterocycle maybe changed into a quaternary heterocycle and, the quaternary heterocyclemay have a counter ion. There is no specific limitation on such counterions, but ordinary anions are permissible. Specific examples thereofinclude F⁻, Cl⁻, Br⁻, I⁻, ClO4⁻, BF4⁻, PF6⁻, OH⁻, SO4²⁻, CH3SO4⁻,toluene sulfonic acid and the like and, among these, Br⁻, I⁻, ClO4⁻,BF4⁻, PF6⁻, CH3SO4⁻ and toluene sulfonic acid are preferable. Further,instead of the counter ion, the heterocycle may be neutralized by anintramolecular or intermolecular acidic group such as a carboxyl groupor the like.

[0055] As the amino group which may be substituted, mentioned are aunsubstituted amino group, a diphenylamino group, a monophenylaminogroup, a dialkylamino group, a monoalkylamino group, an alkylphenylaminogoup, an alkoxyamino group, an acylamino group (for example, abenzoylamino group, an acetylamino group and the like) and the like.

[0056] As the organic metal complex residue, mentioned is a groupobtained by removing a hydrogen atom from an organic complex compound.Examples of such organic complex compounds include ferrocene,ruthenocene, titanocene, zirconocene, phthalocyanine, a rutheniumbipyridyl complex and the like.

[0057] Further, X may be bound to A1 or A2 to form a ring which may besubstituted. Examples of such rings include a benzene ring, anaphthalene ring, an indene ring, a pyridine ring, a pyrazine ring, apyrimidine ring, a quinoline ring, a thiophene ring, an indolenine ring,a benzoindolenine ring, a pyrazole ring, a pyrazolidine ring, a thiazolering, a thiazolidine ring, a benzothiazole ring, an oxazole ring, anoxazolidine, a benzoxazole ring, a pyran ring, a chromene ring, apyrrole ring, an imidazole ring, a benzimidazole ring, an imidazolinering, an imidazolidine, an indole ring, a furan ring, a carbazole ring,a pyran ring, a benzopyran ring, a phthalocyanine ring, a porphyrinring, ferrocene and the like, and these rings each have may behydrogenated. Specific examples thereof, as shown in compound exampleNos. 90 to 92, from 112 to 115, 118 and the like, include an example inwhich, when X is an N-methyl-N-phenylamino group, X forms abenzothiazole ring, a benzoxazole ring or a benzopyrroline ring bybinding to A2 which is a mercapto group, a hydroxy group or an isopropylgroup, respectively, an example in which, when X is anN-ethyl-N-phenylamino group, X forms a quinoline ring by using A2 andmethylene, and the like.

[0058] Further, as a substituent in a case in which the aromatichydrocarbon residue, the heterocycle residue or the organic metalcomplex residue in X is substituted, or as a substituent in a case inwhich a ring formed by any two of the above-described X, A1 or A2 issubstituted, mentioned are same substituents as those on the cyclichydrocarbons described in the paragraph of the above-described A1 or A2,a carbonyl group, a thiocarbonyl group and the like.

[0059] Furthermore, when X, A1 or A2 which forms a ring has a carbonylgroup or a thiocarbonyl group, a ring formed by any two of X, A1 and A2may be a ring substituted by O═ or S═ as a substituent, that is, acyclic ketone or a cyclic thioketone.

[0060] As a preferable substituent in the above-described aromatichydrocarbon residue, heterocyclic residue or organic metal complexresidue or the like in X, or a preferable substituent on a ring formedby using any two of X, A1 and A2, mentioned are an amino group which maybe substituted, an alkyl group which may be substituted, an alkoxylgroup which may be substituted, an acetyl group which may besubstituted, a hydroxyl group, a halogen atom, O═, S═ and the like. As afurther preferable substituent, mentioned are an amino group which maybe substituted, an alkyl group which may be substituted, an alkoxylgroup which may be substituted, O═ and S═. On this occasion, as theamino group which may be substituted, mentioned are a mono- ordialkyl-substituted amino group, a monoalkyl monoaryl-substituted aminogroup, a diaryl-substituted amino goup, a mono- ordialkylene-substituted amino group and the like and, thedialkyl-substituted amino group, the diaryl-substituted amino group arepreferable. As the alkyl group which may be substituted, mentioned arean aryl-substituted alkyl group, a halogen atom-substituted alkyl group,an alkoxyl-substituted alkyl group and the like. As the alkoxyl groupwhich may be substituted, mentioned are an alkoxy-substituted alkoxylgroup, a halogen-substituted alkoxyl group, an aryl-substututed alkoxylgroup and the like.

[0061] A compound represented by the above-described formula (1) is ableto have structural isomers of a cis form, a trans form and the like.However, the compound can favorably be used as a photosensitizing-dyewithout any particular limitation of these structural isomers.

[0062] Among compounds represented by the formula (1), a compound (2) ina case of n=l can be obtained by condensing, for example, an acetic acidderivative represented by the formula (5) and a carbonyl derivativerepresented by the formula (6) optionally in the presence of a basiccatalyst such as piperidine, piperazine or the like in an organicsolvent, preferably a polar solvent such as alcohol, for example,methanol, ethanol, propanol or the like at a reflux temperature.

[0063] Further, a compound (3) in a case of n=2 can similarly beobtained by condensing the acetic acid derivative represented by theformula (5) and a carbonyl derivative represented by the formula (7-1)optionally in the presence of the basic catalyst in a solvent such asthe above-described alcohol or the like.

[0064] Furthermore, a derivative in a case of n=3 or more can beproduced in a same manner by using a carbonyl derivative represented bythe formula (7-2) in place of the carbonyl derivative represented by theformula (7-1). Still further, a derivative in which a ring is formed canbe obtained by condensing an acetic acid derivative and a carbonylderivative having a ring or a carbonyl derivative having a ring. Forexample, the derivative can be obtained by using a compound in which aring is formed by A2 and X in the formula (7-1) or a compound in which aring is formed by either A1 nearer to X and A2 nearer to X, or X and A1or A2 in the formula (7-2).

[0065] Still furthermore, when the acetic acid derivative is poor inreactivity, an ester derivative thereof or a cyano derivative thereof isfirst prepared and, then, hydrolyzed to obtain the above-describedcompound or derivative.

A1-CH₂COOH   Formula (5)

A1-CH₂COOH   Formula (6)

A2-CO—C(A1)=C(A2)-X   Formula (7-1)

A2-CO—C(A1)=C(A2)-C (A1)=C(A2)-X   Formula (7-2)

[0066] wherein A1, A2 and X each represent a same compound as thatdescribed above.

[0067] Specific examples of compounds (dyes) used in the presentinvention will now be shown below.

[0068] Compound examples of derivatives (compounds represented by theabove-described formula (2)) in a case of n=1 in the formula (1) areshown in Table 1. Compound Nos. 1 to 27 in Table 1 show examples ofcompounds represented by the formula (8) mentioed below, whereascompound Nos. 28 to 31 show examples of compounds in which X in theabove-described formula (2) is a 4-(N-ethyl carbazole) group, a group offerrocene, a group of 2-thiophene, a group of ruthenocene and a group ofphthalocyanine, respectively. 4-DMA in Table 1 means 4-dimethyl aniline.Further, examples of R1, R2, B1, B2, B3 and B4 in the formula (8) areshown in Table 1. TABLE 1 (8)

Compound B1 B2 R1 R2 B3 B4 1 CN H CH3 CH3 H H 2 CN H C2H5 C2H5 H H 3 CNH C4H9 C4H9 H H 4 CN H C8H17 C2H5 H H 5 CN H C18H37 C18H37 H H 6 CN HC2H4OCH3 C2H4OCH3 H H 7 CN H Phenyl Phenyl H H 8 CN H p-tolyl p-tolyl HH 9 CN H 4-DMA 4-DMA H H 10 CN H C2H4Cl CH3 H H 11 CN H Phenyl Phenyl HH 12 CN H CH3 CH3 H CH3 13 CN H CH3 CH3 H Cl 14 CN H H COCH3 H H 15 CN HC2H5 C2H5 OCH3 CH3 16 CN H C2H5 C2H5 OCH3 NHCOCH3 17 CN CN C2H5 C2H5 H H18 CN CN C2H4CN 2H4CN H H 19 COOH H C2H4Br C2H4Br H H 20 CONHC2H5 H H HH H 21 CN H H H H H 22 NO2 H CH3 C4H9 H H 23 COOCH3 H CH3 CH3 H H 24COCH3 H C2H5 C2H5 H H 25 CONH2 H C2H5 H H H 26 CN 4-DMA CH3 CH3 H H 27CN Cl CH3 CH3 H H 28 CN H X = 4-(N-ethylcarbazole) 29 CN H X = ferrocene30 CN H X = 2-thiophene 31 CN CN X = ruthenocene 32 CN H X =phtalocyanine

[0069] Examples of derivatives (compounds of the above-described (3)) ofn=2 in the formula (1) are shown in Table 2.

[0070] Compound Nos. 33 to 45 are compound examples represented by theformula (9) described below in a case in which X is a substitutedanilino group in the formula (3) whereas compound Nos. 46 to 49 areexamples of compounds in a case in which X in the formula (3) is a4-(N-ethyl carbazole) group, a group of 2-thiophene, a group offerrocene or a group of phthalocyanine, respectively. Specific examplesof respective group of substituents, R1, R2and C1 to C6, are shown inTable 2. Further, in Table 2,4-dimethyl aniline and 4-diethyl anilineare abbreviated as 4-DMA and 4-DEA, respectively. TABLE 2 (9)

Compound C1 C2 C3 C4 R1 R2 C5 C6 33 CN H H H CH3 CH3 H H 34 COOH H H HCH3 CH3 H H 35 CN H H H C2H4COOH C2H4COOH H H 36 CN H H Cl C2H5 C2H5 H H37 COOH H H H C2H5 C2H5 OCH3 NHCOCH3 38 CN H H H C2H5 C2H5 H OH 39 NO2 HH H CH3 CH3 H H 40 COOH H H H phenyl phenyl H 41 CN H H H phenyl phenylH 42 COOH H H H 4-DEA 4-DEA H H 43 COOH H H 4-DMA CH3 CH3 H H 44 COOC2H5H H H C2H5 C2H5 H H 45 COOPH H H H C8H17 CH3 H H 46 CN H H H X =4-(N-ethlycarbazole) 47 COOH H H H X = 2-thiophene 48 CN H H H X =ferrocene 49 CN H H H X =phtalocyanine

[0071] Other examples of compounds which are derivatives of n=1 and 2 inthe formula (1) are shown below.

[0072] Representative examples of compounds which are derivatives of n=3or more are shown below.

[0073] A dye-sensitized photoelectric conversion device according to thepresent invention is, for example, a device in which a thin film of anoxide semiconductor is produced on a substrate by using oxidesemiconductor fine particles and then a dye is allowed to be adsorbed onthe thus-produced thin film. As fine particles of the oxidesemiconductor, a metal oxide is preferable; specific examples of suchmetal oxides include oxides of titanium, tin, zinc, tungsten, zirconium,gallium, indium, yttrium, niobium, tantalum, vanadium and the like.Among these oxides, oxides of titanium, tin, zinc, niobium, tungsten andthe like are preferable and, above all, titanium oxide is mostpreferable. These oxide semiconductors can be used either alone ormixture thereof. An average particle diameter of the fine particles ofthe oxide semiconductor is ordinarily from 1 nm to 500 nm and preferablyfrom 5 nm to 100 nm. These fine particles of the oxide semiconductor canalso be used in a state of mixtures of large particle diameter ones andsmall particle diameter ones.

[0074] An oxide semiconductor thin film can be produced by a method inwhich oxide semiconductor fine particles are directly vapor-deposited ona substrate to form a thin film, a method in which an oxidesemiconductor thin film is electrically precipitated by using asubstrate as an electrode or a method in which a slurry of semiconductorfine particles to be described below is applied on a substrate, driedand cured or sintered. From the standpoint of performance of an oxidesemiconductor electrode, a method which uses the slurry is preferable.In this method, the slurry can be obtained by dispersing the oxidesemiconductor fine particles which, are in a secondary agglomerationstate by a normal method such that an average primary particle diameterthereof comes to be from 1 nm to 200 nm in a dispersion medium.

[0075] Any dispersion medium of the slurry is usable, so long as it iscapable of dispersing the semiconductor fine particles. Water or anorganic solvent such as an alcohol such as ethanol or the like, a ketonesuch as acetone, acetylacetone or the like or a hydrocarbon such ashexane or the like is used and may be used in mixture thereof and,further, it is favorable to use water from a standpoint that itsuppresses viscosity changes.

[0076] A temperature of sintering a substrate which has been coated withthe slurry is ordinarily 300° C. or more, preferably 400° C. or more anda maximum allowable temperature thereof is approximately not greaterthan a melting point (softening point) of the substrate, ordinarily 900°C. as an upper limit and preferably600° C. or less. Further, a period oftime of sintering the substrate is not particularly limited, but ispreferably within about 4 hours. Thickness of the thin film on thesubstrate is ordinarily from 1 μm to 200 μm and preferably from 5 μm to50 μm.

[0077] The oxide semiconductor thin film may be subjected to a secondarytreatment. Namely, for example, the thin film can directly be immersedtogether with the substrate in a solution of an alkoxide, a chloride, anitride, a sulfide or the like of the same metal as the semiconductorand, then, dried or sintered again to enhance performance of thesemiconductor thin film. Examples of such metal alkoxides includetitanium ethoxide, titanium isopropoxide, titanium t-butoxide,n-dibutyl-diacetyl tin and the like and an alcoholic solution thereof isused. Examples of such chlorides include titanium tetrachloride, tintetrachloride, zinc chloride and the like and an aqueous solutionthereof is used.

[0078] Next, a method to adsorb a dye on the oxide semiconductor thinfilm is explained. As the above-described method for adsorbing the dyethereon, mentioned is a method in which a substrate on which theabove-described oxide semiconductor thin film has been provided isimmersed in a solution obtained by dissolving a dye in a solvent capableof dissolving the dye or in a dispersion liquid obtained by dispersing adye which has a low solubility. A concentration of the dye in thesolution or the dispersion liquid is appropriately determined dependingon dyes. The semiconductor thin film formed on the substrate is immersedin the solution. An immersion temperature is approximately from normaltemperature up to a boiling point of the solvent and, further, animmersion period of time is from about 1 hour to about 48 hours.Specific examples of solvents to be used in dissolving the dye includemethanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamideand the like. A concentration of the dye in the solution is ordinarilyfavorably from 1×10⁻⁶ M to 1 M and preferably from 1×10⁻⁶ M to 1×10⁻¹ M.In such a way as described above, a photoelectric conversion device ofthe oxide semiconductor thin film sensitized with the dye can beobtained.

[0079] The dye to be adsorbed may be composed of one type or a mixtureof two or more types. When the dyes are mixed, the dyes which have anacrylic acid part according to the present invention may be mixed thereamong or mixed with any one of other dyes and metal complex dyes.Particularly, by mixing dyes having different absorption wavelengthsfrom one another, a wider absorption wavelength can be utilized and, asa result, a solar cell having high conversion efficiency can beobtained. By utilizing three or more types of dyes, it becomes possibleto even fabricate an optimum solar cell.

[0080] As examples of such metal complex dyes to be utilized for themixture, there is no particular limitation thereon, but a rutheniumcomplex which have been disclosed in J. Am. Chem. Soc., 115, 6382 (1993)or JP-A-2000-26487, phthalocyanine, porphyrin and the like arepreferable. Examples of organic dyes to be utilized for the mixtureinclude dyes such as metal-free phthalocyanine, metal-free porphyrin, ormethine-type dyes such as cyanine, merocyanine, oxonol, a triphenylmethane type and the like, a xanthene type, an azo type, ananthraquinone type and the like. Among these dyes, the ruthenium complexand methine-type dyes such as merocyanine and the like are preferable. Aratio of the dyes to be mixed is not particularly limited and isoptimized according to respective dyes. However, it is ordinarilypreferable to mix them in the range of between each equivalent mol andabout 10% mol or more for a dye. When mixed dyes are adsorbed on thethin film of the oxide semiconductor fine particles by using a solutionin which such mixed dyes are mix-dissolved or dispersed, a concentrationof entire dyes in the solution may be same as that in a case in whichonly one type of dye is adsorbed.

[0081] When the dye is adsorbed on the thin film of the oxidesemiconductor fine particles, it is effective to adsorb the dye in thepresence of an inclusion compound in order to prevent dyes fromassociating with each other. Examples of such inclusion compoundsinclude steroid-type compounds such as cholic acid and the like, crownethers, cyclodextrin, calixarene, polyethylene oxide and the like.Cholic acid, polyethylene oxide and the like are preferable. Further,after the dye is adsorbed thereon, a surface of a semiconductorelectrode may be treated with an amine compound such as4-t-butylpyridine or the like. As a method for such treatment, forexample, a method in which a substrate having a thin film, on which thedye is adsorbed, of the semiconductor fine particles is immersed in anethanol solution of an amine or the like can be adopted.

[0082] The solar cell according to the present invention comprises aphotoelectric conversion device electrode in which the dye is adsorbedon the above-described oxide semiconductor thin film, a counterelectrode and a redox electrolyte or a hole transfer material. The redoxelectrolyte may be a solution in which a redox pair is dissolved in asolvent, a gel electrolyte that a polymer matrix is impreganated with aredox pair or a solid electrolyte such as a fused salt. Examples of holetransfer materials include an amine derivative, an electricallyconductive polymer such as polyacetylene, polyaniline, polythiophene orthe like, a material using a discotic liquid crystal phase such aspolyphenylene and the like. The counter electrode to be used ispreferably an electrode which has electric conductivity andcatalytically acts on a reduction reaction of the redox electrolyte. Forexample, a material in which platinum, carbon, rhodium, ruthenium or thelike is vapor-deposited on glass or a polymer film, or electricallyconductive fine particles are applied thereon can be used.

[0083] Examples of redox electrolytes to be used in solar cellsaccording to the present invention include a halogen redox electrolytecomprising a halogen compound and halogen molecule having a halogen ionas a counter ion, a metal oxidation-reduction type electrolyte of ametal complex or the like such as ferrocyanate-ferricyanate,ferrocene-ferricinium ion or the like and an aromatic redox electrolytesuch as alkylthiol-alkyldisulfide, a viologen dye, hydroquinone-quinoneor the like, and the halogen redox electrolyte is preferable. As thehalogen molecule in the halogen redox electrolyte comprising halogencompound-halogen molecule, mentioned is, for example, an iodinemolecule, a bromine molecule or the like, and the iodine molecule ispreferable. Further, examples of the halogen compounds having a halogenion as a counter ion include a halogenated metal salt, for example, LiI,NaI, KI, CsI, CaI₂ or the like, or an organic quaternary ammonium saltof halogen such as tetraalkylammonium iodide, imidazolium iodide,pyridinium iodide or the like, and a salt-type compound having theiodine ion as a counter ion is preferable. Examples of such salt-typecompounds having the iodine ion as a counter ion include lithium iodide,sodium iodide, a trimethyl iodide ammonium salt and the like.

[0084] Further, when the redox electrolyte is constituted in a solutionstate containing itself, an electrochemically inert solvent is used as asolvent. Examples of such solvents include acetonitrile, propylenecarbonate, ethylene carbonate, 3-methoxypropionitrile,methoxyacetonitrile, ethylene glycol, propylene glycol, diethyleneglycol, triethylene glycol, γ-butyrolactone, dimethoxyethane, diethylcarbonate, diethyl ether, diethyl carbonate, dimethyl carbonate,1,2-dimethoxy ethane, dimethyl formamide, dimethyl sulfoxide,1,3-dioxolane, methyl formate, 2-methyl tetrahydrofuran,3-methoxy-oxaziridine-2-one, sulfolane, tetrahydrofuran, water and thelike. Among these solvents, particularly, acetonitrile, propylenecarbonate, ethylene carbonate, 3-methoxypropionitrile,methoxyacetonitrile, ethylene glycol, 3-methoxyoxaziridine-2-one and thelike are preferable. These solvents may be used either alone or in anycombination of two or more types. In a case of the gel electrolyte,mentioned is a gel electrolyte which uses a polyacrylate orpolymethacrylate resin or the like as a matrix. A concentration of theredox electrolyte is ordinarily from 0.01% by weight to 99% by weightand preferably from about 0.1% by weight to about 90% by weight.

[0085] The solar cell according to the present invention can be obtainedby arranging the counter electrode against an electrode of thephotoelectric conversion device adsorbing the dye in the oxidesemiconductor thin film on the substrate such that the electrode of thephotoelectric conversion device is interposed, and filling a solutioncontaining the redox electrolyte between the electrode of thephotoelectric conversion device and the counter electrode.

EXAMPLES

[0086] The present invention is now more specifically described withreference to Examples. However, it should be noted that these Examplesshould not be interpreted as limiting the present invention. Unlessstated otherwise, all parts and percentages in these Examples are givenby mass.

Synthesis Example 1

[0087] One part of cyanoacetic acid and 2 parts of N,N-diethylaminobenzaldehyde were dissolved in 10 parts of ethanol and then 0.6 part ofpiperazine anhydride was added thereto dropwise. The resultant mixturewas reacted under reflux for 2 hours and then cooled to obtain a solid.The thus-obtained solid was filtered, washed and dried, and thenrecrystallized with a mixed solvent of ethanol and hexane(ethanol:hexane=3:1), filtered, washed and thereafter dried to obtain2.1 parts of a compound (2).

[0088] Melting point: from 185° C. to 187° C. (mel-temp used)

[0089] 1H-NMR(δ(ppm): d6-DMSO)): 1.12(t, CH3, 6H), 3.43(q, CH2, 4H),6.77(d, arom, 2H), 7.83(d, arom, 2H), 7.89(s, ═CH—, 1H)

[0090] Mass spectrometry: M-1=243 (mw=244) (measured by using TOF MSavailable from Micromass Ltd. Under ESI negative mode)

[0091] Absorption maximum (methanol): 406 mm

[0092] Luminescence maximum (methanol): 476 mm

Synthesis Example 2

[0093] 0.8 part of malonic acid and 1 part of 4-dimehylamino cinnamicaldehyde were dissolved in 10 parts of ethanol and, then, 0.3 part ofpiperazine anhydride was added thereto dropwise. The resultant mixturewas reacted under reflux for 2 hours and then cooled to obtain a solid.The thus-obtained solid was filtered, washed and dried, and thenrecrystallized with a mixed solvent of ethanol and hexane, filtered,washed and thereafter dried to obtain 1.0 parts of a compound (34).

[0094] Melting point: from 160° C. to 165° C. (mel-temp used)

[0095] 1H-NMR(δ(ppm): d6-DMSO)): 3.02(s, CH3, 6H), 6.74(d, arom, 2H),7.00(d, ═CH—, 1H), 7.40(d,arom, 2H), 7.65(d, ═CH—, 1H), 8.11(dd, ═CH—,1H)

[0096] Mass spectrometry: M-1=260 (mw=261) (measured by using TOF MS ESIavailable from Micromass Ltd. under negative mode)

[0097] Absorption maximum (methanol): 429 mm

[0098] Luminescence maximum (methanol): 562 mm

[0099] Compounds described below were synthesized by using materialscorresponding to respective target compounds in a same manner as in theabove-described synthesis examples. Compound numbers and respectivephysical properties are shown in Table 3. TABLE 3 Syn- thesis MeltingAbsorption Luminescence Mass spectrometry example point maximum maximum(molecular weight) 1 212-214 416 nm 469 nm M − 1 = 215(216) 7 230-235418 nm 540 nm M − 1 = 339(340) 28 165-166 381 nm 489 nm M − 1 = 289(290)29 155-160 317 nm — M − 1 = 280(281) 33 165-170 433 nm 565 nm M − 1 =241(242)

[0100] Example

[0101] In regard to Examples from 1 to 21, a dye having an acrylic acidpart was dissolved in EtOH in a concentration of 3×10⁻⁴ M. In regard toExamples from 22 to 25, dyes were dissolved in EtOH such that each dyecame to be in a concentration of 1.5×10⁻⁴ M. In regard to Example 26,dyes were dissolved in EtOH such that each dye came to be in aconcentration of 1×10⁻⁴ M. In regard to Example 27, dyes were dissolvedin EtOH such that each dye came to be in a concentration of 7.5×10⁻³ M.In each of the resultant solutions, a porous substrate (semiconductorthin film electrode prepared by the steps of: dispersing titaniumdioxide P-25 available from Nippon Aerosil Co., Ltd. in an aqueoussolution of nitric acid, applying the thus-dispersed titanium dioxide ona transparent electrically conductive glass electrode in a thickness of50 μm; and sintering the resultant electrode at 450° C. for 30 minutes)was immersed at room temperature for from 3 hours to one night toadsorbed the dye therein, washed with a solvent and dried to obtain aphotoelectric conversion device of a dye-sensitized semiconductor thinfilm. Further, in Examples 2, 7, 9, 13, 16, 17, 18, 22, 26 and 27, anaqueous solution of 0.2 M titanium tetrachloride was added dropwise to atitanium oxide thin film portion of the semiconductor thin filmelectrode, it left to stand at room temperature for 24 hours, and thenwashed with water and sintered again at 450° C. for 30 minutes to obtaina titanium tetrachloride-treated semiconductor thin film electrode. Thedye was adsorbed in the thus-obtained titanium tetrachloride-treatedsemiconductor thin film electrode in the same manner.

[0102] Further, in Examples 4 and 10, when the dye solution wasprepared, cholic acid was added as an inclusion compound such that itbecame to be 3×10⁻⁵ M at the time the dye was adsorbed and, then, theresultant dye solution was adsorbed in the semiconductor thin film toobtain a cholic acid-treated dye-sensitized semiconductor thin film. Anelectrically conductive glass whose surface had been sputtered byplatinum was fixed such that the thus-obtained dye-sensitizedsemiconductor thin film is interposed and, then, a gap generatedtherebetween was filled with an electrolyte-containing solution. Threetypes of such electrolyte-containing solutions were prepared. Anelectrolyte-containing solution A was prepared by dissolving iodine,lithium iodide, 1,2-dimethyl-3-n-propyl imidazolium iodide, t-butylpyridine in 3-methoxypropionitrile such that concentrations thereof in3-methoxypropionitrile became 0.1 M, 0.1 M, 0.6 M and 1 M, respectively.An electrolyte-containing solution B was prepared by dissolving iodineand tetra-n-propyl ammonium iodide in a mixed solution of ethylenecarbonate and acetonitrile in a mixing ratio of 6 to 4 such thatconcentrations thereof in the mixed solution became 0.02 M and 0.5 M,respectively. An electrolyte-containing solution C was prepared bydissolving iodine and lithium iodide in propylene carbonate such thatconcentrations thereof became 0.05 M and 0.55 M in propylene carbonate,respectively.

[0103] A size of a cell used for measurements was set such that anexecution part thereof was 0.25 cm². A light source was set to be 100mW/cm through an AM 1.5 filter using a 500 W xenon lamp. Short circuitcurrent, open circuit voltage, conversion efficiency and a form factorwere measured by using a potentiogalvanostat.

[0104] Further, measurements on Comparative Examples were conducted in asame manner as in Example 1 by using the following Ru complex dye (131)and a merocyanine dye: TABLE 4 (131)

(132)

Short Open TiCl4 Cholic Compound circuit circuit Conversion treatment ofacid Electrolytic No. current voltage efficiency thin film treatmentsolution Example  1 1 5.7 0.56 1.5 Untreated Untreated B  2 2 5.1 0.742.2 Treated Untreated B  3 7 5.4 0.63 2.1 Untreated Untreated A  4 7 4.70.67 1.8 Untreated Treated B  5 10 4.6 0.65 2.0 Untreated Untreated B  612 5.5 0.67 2.3 Untreated Untreated B  7 13 5.0 0.74 2.3 TreatedUntreated B  8 28 4.5 0.65 1.8 Untreated Untreated B  9 28 4.3 0.74 2.0Treated Untreated B 10 29 0.4 0.46 0.1 Untreated Treated A 11 33 7.10.62 2.3 Untreated Untreated C 12 34 7.3 0.59 2.1 Untreated Untreated C13 40 6.9 0.58 2.5 Treated Untreated B 14 41 5.7 0.57 2.1 UntreatedUntreated B 15 50 5.0 0.53 1.7 Untreated Untreated B 16 86 2.3 0.66 1.0Treated Untreated B 17 88 2.8 0.50 0.9 Treated Untreated B 18 90 3.20.67 1.4 Treated Untreated B 19 106 6.3 0.56 2.0 Untreated Untreated B20 107 4.9 0.58 1.9 Untreated Untreated A 21 10 4.6 0.65 2.0 UntreatedUntreated B 22 2 + 131 12.3 0.70 5.4 Treated Untreated B 23 2 + 41 9.60.61 2.4 Untreated Untreated B 24 33 + 41 9.3 0.55 2.6 UntreatedUntreated B 25 40 + 132 9.2 0.64 3.8 Untreated Untreated B 26 7 + 41 +10.5 0.66 4.1 Treated Untreated B 132 27 2 + 7 + 10.1 0.67 4.2 TreatedUntreated B 41 + 132 Comparative Example  1 131 11.0 0.71 4.5 UntreatedUntreated B  2 132 6.3 0.56 2.4 Untreated Untreated B

[0105] Industrial Applicability

[0106] In a dye-sensitized photoelectric conversion device according tothe present invention, a solar cell having high conversion efficiencywas able to be provided by using a dye having an acrylic acid part.

1. A photoelectric conversion device, characterized by comprising oxidesemiconductor fine particles sensitized with a dye having an acrylicacid part.
 2. A photoelectric conversion device, characterized bycomprising oxide semiconductor fine particles sensitized with a dyerepresented by the following formula (1) having an acrylic acid part:

wherein A1 and A2 each independently represent a carboxyl group, a cyanogroup, an alkoxycarbonyl group, an acyl group, a nitro group, a cyclichydrocarbon residue which may be substituted, a heterocyclic residuewhich may be substituted, an amino group which may be substituted, ahydroxyl group, a hydrogen atom, a halogen atom or an alkyl group whichmay be substituted; X represents an aromatic hydrocarbon residue whichmay be substituted, a heterocyclic residue which may be substituted, anorganic metal complex residue which may be substituted or an amino groupwhich may be substituted; n represents an integer from 1 to 6; when n is2 or more and a plurality of A1 and a plurality of A2 are present, eachA1 and each A2 independently represent any one of said groups which maybe same with or different from each other and further two among of A1sor each A1 in a plurality of A1, A2 or each A2 in a plurality of A2 andX may be bound together to form a ring which may be substituted,
 3. Thephotoelectric conversion device as set forth in claim 2, wherein n isfrom 1 to 3 in the formula (1).
 4. The photoelectric conversion deviceas set forth in claim 2, characterized in that at least one of A1 and A2or, when a plurality of A1 and a plurality of A2 are present, at leastone thereof is a cyano group or a carboxyl group in the formula (1). 5.The photoelectric conversion device as set forth in claim 4,characterized by that A1 in the formula (1) is a cyano group or acarboxyl group wherein the A1 binds to the same carbon atom as that thecarboxyl group in an acrylic part is bound to.
 6. The photoelectricconversion device as set forth in any one of claims 2 to 5, wherein thearomatic hydrocarbon residue in X in the formula (1) is an aromatichydrocarbon residue having a substituted amino group.
 7. Thephotoelectric conversion device as set forth in any one of claims 2 to5, wherein the heterocyclic residue is a heterocyclic residue which is a5- or 6-membered ring cotaining from 1 to 3hetero atoms and may besubstituted, or a heterocyclic residue comprising a condensed ring,having from 8 to 15 carbon atoms, which contains a 5- or 6-memberedheterocycle containing from 1 to 3 hetero atoms.
 8. The photoelectricconversion device as set forth in claim 6, wherein the aromatichydrocarbon residue in X of the formula (1) is an aromatic hydrocarbonresidue comprising an aromatic ring having from 6 to 16 carbon atoms. 9.The photoelectric conversion device as set forth in claim 8, wherein thearomatic hydrocarbon residue in X of the formula (1) is a phenyl grouphaving a mono- or di-(C1 to C4) alkyl-substituted amino group, whereinsaid phenyl group may further be substituted by one or two substituentsselected from the group consisting of a halogen atom, an alkyl grouphaving from 1 to 4 carbon atoms and an alkoxy group having from 1 to 4carbon atoms.
 10. The photoelectric conversion device as set forth inany one of claims 1 to 9, characterized by comprising oxidesemiconductor fine particles comprising at least one dye having anacrylic acid part and sensitized with simultaneously using two or moretypes of sensitizing-dyes.
 11. The photoelectric conversion device asset forth in claim 9, characterized by comprising oxide semiconductorfine particles sensitized with simultaneously using three or more typesof sensitizing-dyes.
 12. The photoelectric conversion device as setforth in any one of claims 1 to 11, wherein the oxide semiconductor fineparticles comprise titanium dioxide as an essential component.
 13. Thephotoelectric conversion device as set forth in any one of claims 1 to12, wherein a dye is adsorbed to the oxide semiconductor fine particlesin the presence of an inclusion compound.
 14. A solar cell,characterized by comprising the photoelectric conversion device as setforth in any one of claims 1 to 13.